Compounds (η 5 -C 5 H 4 CH 2 CH 2 OCH 3 )TiCl 3 , (η 5 -C 5 H 4 CH 2 CH 2 OCH 3 ) 2 TiCl 2 and (η 5 -C 5 H 4 CH 2 CH 2 OCH 3 ) (η 5 -C 5 H 5 )TiCl 2 react with BBr 3 to give a high yield of titanium compounds containing cyclopentadienyl ligands with bromoethyl substituents, (η 5 -C 5 H 4 CH 2 CH 2 Br)TiBr 3 (1), (η 5 -C 5 H 4 CH 2 CH 2 Br) 2 TiBr 2 (3) and (η 5 -C 5 H 4 CH 2 CH 2 Br)(η 5 -C 5 H 5 )TiBr 2 (4), respectively. Hydrolysis of 1 in the presence of tert-butylamine affords cyclo-[(η 5 -C 5 H 4 CH 2 CH 2 Br)TiBr(μ-O)] 4 (2) in quantitative yield. The molecular structure of 2 was determined by X-ray diffraction.